Thiadiazolyl-glyoxylonitrile-2-oxime ether derivatives for protecting plant crops

ABSTRACT

A process for protecting cultivated plants against aggressive agricultural chemicals is described in which oxime derivatives of the formula ##STR1## are used as antidotes. Either the cultivated area for the cultivated plants or the cultivated plants themselves or parts of the plant (seeds, tubers, stem parts and the like), as desired, can be treated with these oxime derivatives, which are used as a dressing. 
     Ar is a phenyl radical of the formula ##STR2## or Ar is also a 5-membered to 10-membered heterocyclic radical which contains not more than three identical or different hetero-atoms N, O and/or S and which can be bonded via a C 1  - to C 3  -aliphatic chain to the remainder of the molecule and which is substituted by R 1 , R 2  or R 3  and can be substituted by oxo or thiono; X is hydrogen, CN, halogen, C 1  -C 10  -alkyl, lower alkanoyl, --COOH, a carboxylic acid ester of a carboxamide radical; and Q is hydrogen, lower alkyl, which can be interrupted by hetero-atoms or substituted by halogen or cyano, lower alkenyl or halogenoalkenyl, lower alkynyl, C 3  -C 7  cycloalkyl, which is unsubstituted or substituted by halogen, or a lower alkanecarboxylic acid ester group, a lower alkanecarboxylic acid thioester group, a lower alkanecarboxamide group, an aliphatic acyl radical, an araliphatic, cycloaliphatic or substituted or unsubstituted aromatic or heterocyclic acyl radical, an alkylsulfonyl radical, a sulfonamide radical, a metal salt, a quaternized ammonium salt or an aliphatic, araliphatic, cycloaliphatic or substituted or unsubstituted aromatic or heterocyclic carbonic acid, thiocarbonic acid or carbamoyl radical.

This is a divisional of application Ser. No. 70,288 filed on Aug. 28,1979, now U.S. Pat. No. 4,347,372.

The present invention relates to oxime derivatives of the generalformula I ##STR3## and their preparation and to novel agents based onthese compounds and also to the use of such compounds and agents forprotecting cultivated plants against aggressive agricultural chemicals.

The active substances have the formula I, in which Ar is a phenylradical of the formula ##STR4## in which R₁ is hydrogen, halogen, loweralkyl, C₁ -C₁₀ -alkoxy or a phenoxy radical which is in thepara-position and is unsubstituted or at most disubstituted by halogen,--CN, NO₂ or CF₃, R₂ is hydrogen, halogen, NO₂, lower alkyl,halogenoalkyl or lower alkoxy, R₃ is hydrogen or R₄ and R₄ is phenyl,halogenophenyl, benzyl, halogenobenzyl, cyclohexyl, OH, CN,halogenoalkoxy, lower alkanoyl, lower carbalkoxy, lower alkoxycarbonyl,lower alkoxycarbonyloxy, lower alkylcarbamoyloxy, lower alkylthio, loweralkylsulfonyl, phenalkoxy, NH₂, --NH--(lower alkyl), --N(lower alkyl)₂,lower alkanoylamino, benzoylamino, carboxamide or sulfonamide, or Ar isalso a 5-membered to 10-membered heterocyclic radical which contains notmore than three identical or different hetero-atoms, N, O and/or S andwhich can be bonded via a C₁ - to C₃ -aliphatic chain to the remainderof the molecule and which is substituted by R₁, R₂ or R₃ and can besubstituted by oxo or thiono, with the proviso that, if Q is not H and afuran or thiophen ring is present, the latter carries at least onesubstituent other than hydrogen and that, in the case of a furan orthiophen ring which is monosubstituted or disubstituted by halogen,nitro or lower alkyl, this ring is substituted by a third substituentother than hydrogen, X is hydrogen, CN, halogen, C₁ -C₁₀ -alkyl, loweralkanoyl, --COOH, a carboxylic acid ester or a carboxamide radical and Qis hydrogen, lower alkyl, which can be interrupted by hetero-atoms orsubstituted by halogen or cyano, lower alkenyl or halogenoalkenyl, loweralkynyl, C₃ -C₇ cycloalkyl, which is unsubstituted or substituted byhalogen, or a lower alkanecarboxylic acid ester group, a loweralkanecarboxylic acid thioester group, a lower alkanecarboxamide group,an aliphatic acyl radical, an araliphatic, cycloaliphatic or substitutedor unsubstituted aromatic or heterocyclic acyl radical, an alkylsulfonylradical, a sulfonamide radical, a metal salt, a quaternised ammoniumsalt or an aliphatic, araliphatic, cycloaliphatic or substituted orunsubstituted aromatic or heterocyclic carbonic acid, thiocarbonic acidor carbamoyl radical.

In the formula I, halogen is to be understood as meaning fluorine,chlorine, bromine or iodine.

Carboxylic acid esters and carboxylic acid thioesters are carboxylicacid lower alkyl esters and carboxylic acid lower alkyl thioesters. Acylradicals are to be understood as meaning carboxylic acid radicals. Inaddition to --CONH₂ and --SO₂ --NH₂, carboxamides and sulfonamides arealso monoalkyl-substituted or symmetrically or asymmetricallydialkyl-substituted or N-alkyl-N-alkoxy-substituted amides, in which thealkyl groups are lower alkyl.

The term alkyl, on its own or as part of a substituent, comprisesbranched or unbranched C₁ -to C₁₀ -alkyl groups; lower alkyl, on its ownor as part of a substituent, is C₁ -C₄ alkyl. Examples are methyl,ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl and tert.-butyland also the higher homologues amyl, isoamyl, hexyl, heptyl, octyl,nonyl and decyl, including the isomers thereof. Accordingly, alkanoylsor cyanoalkyls contain an additional C atom. Correspondingly, loweralkenyl or alkynyl groups contain not more than 4 C atoms.

The term aliphatic group includes both saturated (alkyls) andunsaturated (alkenyls, alkadienyls and alkynyls), halogen-substitutedand cyano-substituted radicals, and radicals interrupted by oxygen,which contain not more than 10 carbon atoms.

The term aromatic group comprises phenyl and naphthyl.

An araliphatic radical comprises a phenyl or naphthyl which isunsubstituted or monosubstituted to trisubstituted and is bonded vialower alkyl or lower alkenyl to the remainder of the molecule. Examplesare the parent structures benzyl, phenethyl, phenylallyl and homologues.

The term heterocyclic acyl radical comprises 5-membered or 6-memberedheterocyclic carboxy compounds with a ring hetero-atom from the seriescomprising N, O or S. Examples are the radicals of furancarboxylic acid,thiophencarboxylic acid, nicotinic acid, isonicotinic acid and others.

A 5-membered to 10-membered heterocyclic radical Ar can be monocyclic orbicyclic.

Examples from the series of monocyclic rings are pyrrole, thiophen,furan, imidazole, pyrazole, oxazole, thiazole, thiadiazole, triazole,pyridine, pyrazine, pyramidine, pyridazine and triazines and also theirpartially or completely hydrogenated derivatives; further radicals ofthis series are azetidine, aziridine, morpholine, thiomorpholine,oxathiine, dioxan, dioxolane, dithiolane, dithiane and others.

Radicals of the bicyclic series of 5-membered to 10-memberedheterocyclic structures are the ring systems listed above in combinationwith a fused benzene ring (for example benzofuran, indole,benzodioxolane, benzthiazole, benzoxazole, quinoline, benzothiadiazine,benzotriazine and others) and also those containing hetero-atoms in bothrings (for example quinolizidine, purine and the like).

Further heterocyclic ring systems are formed by the incorporation of oxoand/or thiono, for example hydantoin, thiohydantoin, triazinone,coumarin, pyrone, maleic acid hydrazide, maleic anhydride, glutaricanhydride, barbituric acid and others.

N-Heterocyclic structures also include N-oxides,

Cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyland cycloheptyl. Cycloaliphatic radicals correspond to these ringsystems but, in addition, can also contain one or several double bonds,depending on what is possible.

Metal salts are to be understood as meaning cations of groups I to IV ofthe periodic table and also heavy metal salts. Examples are Na, K, Ca,Mg, Al, Zn, Cu, Fe, Mn, Co and Ni.

Quaternary ammonium salts contain, as identical or differentsubstituents, hydrogen, C₁ -C₁₂ alkyl, lower hydroxyalkyl, benzyl, aminoand di-lower alkylamino, or form, from two valencies and the N atom, a5-membered or 6-membered heterocyclic ring which can contain a furtherhetero-atom N, O or S.

Oximes of the formula I are outstandingly suitable for protectingcultivated plants such as rice, maize and species of cereal (cultivatedmillet, wheat, rye, barley and oats) against attack by agriculturalchemicals which are aggressive to plants, especially by herbicidesbelonging to very diverse categories or substances, if these do not actselectively or do not act sufficiently selectively, i.e. damage not onlythe weeds to be combated but also the cultivated plants to a greater orlesser extent.

Diverse substances which are capable of specifically antagonising theharmful action of a herbicide on the cultivated plants, i.e. ofprotecting the cultivated plant without noticeably influencing theherbicidal action on the weeds to be combated, have already beenproposed as antidotes. Depending on its characteristics, an antidote ofthis type, which is also termed a safener, can be used for thepre-treatment of the seed of the cultivated plant (dressing of the seedor of the cuttings) or before sowing, in the seed furrows, or as a tankmixture, on its own or together with the herbicide, before or afteremergence of the plants.

Thus, British Patent Specification No. 1,277,557 describes the treatmentof seeds and seedlings of wheat and sorghum with certain oxamic acidesters and amides before attack byN-methoxymethyl-2',6'-diethyl-chloroacetanilide (Alachlor). Otherliterature sources (German Offenlegungsschrift No. 1,952,910, GermanOffenlegungsschrift No. 2,245,471 and French Patent Specification No.2,021,611) propose antidotes for the treatment of cereals, maize seedand rice seed in order to protect them against attack by herbicidalthiolcarbamates. In German Patent Specification No. 1,576,676 and U.S.Pat. No. 3,131,509, hydroxy-amino-acetanilides and hydantoins areproposed for the protection of cereal seeds against carbamates such asIPC, CIPC and the like. However, on further development all of thesepreparations have proved inadequate.

Preferred antidotes are those compounds of the formula I in which Ar isa substituted or unsubstituted pyridine radical, a substituted orunsubstituted thiophen radical, a substituted or unsubstitutedbenzoxazole, benzthiazole or benzimidazole radical, a substituted orunsubstituted thiadiazole radical or a substituted or unsubstitutedimidazole, imidazoline or imidazolidine radical.

A preferred group of compounds comprises those of the formula ##STR5##in which X is as defined under formula I and R₂₇ is a halogen atom,preferably chlorine or bromine, and in which the three hydroxyl groupsare in the free form or in the form of NH₄ ⁺ or of metal salts or arepartially or completely carbamoylated and/or etherified by loweraliphatic groups. Important carbamate groupings on one, two or all threeof the hydroxyl groups are those which are formed by reaction of a C₁-C₆ alkyl isocyanate or of a phenyl isocyanate which is unsubstituted orsubstituted by halogen or lower alkyl. A particularly preferred antidoteis the compound of the formula ##STR6## which is listed under No. 198 inthis specification, and also further compounds of this type in which Xis not hydrogen and which contain three lower alkylcarbamoyloxy groupsof an analogous type.

Another preferred group of compounds comprises those of the formula##STR7## in which X is CN or a carboxylic acid ester, Q is lower alkyl,which can be interrupted by hetero-atoms or substituted by halogen orcyano, lower alkenyl or halogenoalkenyl, lower alkynyl, an aliphatic,araliphatic, cycloaliphatic or substituted or unsubstituted aromatic orheterocyclic acyl radical, an alkylsulfonyl radical or an aliphatic,araliphatic, cycloaliphatic or substituted or unsubstituted aromatic orheterocyclic carbamoyl radical and R₁, R₂ and R₃ are as defined forformula I. Especially preferred are those in which R₁, R₂ and R₃ arehydrogen.

Another preferred group of compounds comprises those of the formula##STR8## in which X is methyl, CN or a carboxylic acid ester, Q is loweralkyl, which can be interrupted by hetero-atoms or substituted byhalogen or cyano, lower alkenyl or halogenoalkenyl, lower alkynyl, analiphatic, araliphatic, cycloaliphatic or substituted or unsubstitutedaromatic or heterocyclic acyl radical, an alkylsulfonyl radical or analiphatic, araliphatic, cycloaliphatic or substituted or unsubstitutedaromatic or heterocyclic carbamoyl radical and R₁, R₂ and R₃ are asdefined for formula I. Especially preferred are those in which R₁, R₂and R₃ are hydrogen.

Another preferred group of compounds comprises those of the formula Iwherein Ar is the group ##STR9## X is hydrogen or Q is hydrogen or analiphatic carbamoyl radical.

Another preferred group of compounds comprises those of the formula Iwherein Ar is the group ##STR10## which is substituted by lower alkoxy,lower alkylthio, lower alkylsulfinyl, lower alkylsulfonyl or phenyl, Qis hydrogen, lower alkyl, which can be interrupted by heteroatoms orsubstituted by halogen or cyano, or an aliphatic acyl radical, and X isas defined for formula I. Especially preferred are those wherein X isCN, halogen or carboxylic ester.

Another preferred group of compounds comprises those of the formula I,wherein Ar is the group ##STR11## which can be substituted by halogenand in which Y is lower alkyl, lower alkoxycarbonyl or phenyl, Q ishydrogen or an aliphatic, araliphatic, cycloaliphatic or substituted orunsubstituted aromatic or heterocyclic acyl or carbamoyl radical, and Xis as defined for formula I.

Another preferred group of compounds comprises those of the formula I,wherein Ar is the group ##STR12## which can be monosubstituted ordisubstituted by halogen, Q is hydrogen, and X is as defined for formulaI.

Another preferred group of compounds comprises those of the formula I,wherein Ar is the group ##STR13## in which R₁ is hydrogen, halogen orlower alkyl, R₂ is hydrogen, halogen, lower alkyl or halogenalkyl and R₃is lower alkoxycarbonyloxy, lower alkylcarbamoyloxy or lower carbalkoxyand X is C₁ -C₁₀ -alkyl, CN or carboxylic acid ester, and Q is asdefined in formula I.

Another preferred group of compounds comprises those of the formula I,wherein Ar is the group ##STR14## in which Z₁ and Z₂ independently ofone another are lower alkylcarbamoyl, cycloalkylcarbamoyl,arylcarbamoyl, lower alkyl, lower alkenyl, lower alkynyl or lowerhalogenoalkyl, X is hydrogen, and Q is hydrogen, NH₄ ⁺, metal salt,lower alkylcarbamoyl, cycloalkylcarbamoyl, arylcarbamoyl or a loweraliphatic residue.

Surprisingly, oximes of the formula I have the property of protectingcultivated plants against the attack of agricultural chemicals which areaggressive to plants, especially against herbicides of very diversecategories of substances, including 1,3,5-triazines, 1,2,4-triazinones,phenylurea derivatives, carbamates, thiolcarbamates, phenoxyacetic acidesters, phenoxypropionic acid esters, halogenoacetanilides,halogenophenoxyacetic acid esters, substituted phenoxyphenoxy-aceticacid esters and -propionic acid esters, substitutedpyridinoxyphenoxyacetic acid esters and -propionic acid esters, benzoicacid derivatives and the like, if these are not tolerated or are notadequately tolerated by the cultivated plants.

Depending on the intended application, an antidote, of this type, of theformula I can be employed for the pre-treatment of the seed of thecultivated plant (dressing of the seed or of the cuttings) or can beadded to the soil before or after sowing or can be applied, on its ownor together with the herbicide, before or after emergence of the plants.In principle, therefore, the treatment of the plant or of the seed withthe antidote can be effected independently of the time at which thephytotoxic chemicals are applied. It can, however, also be carried outat the same time (tank mixture). Pre-emergence treatment includes bothtreatment of the cultivated area before sowing (ppi="pre plantincorporation") and treatment of the cultivated areas after sowing butbefore emergence of the plants.

The amounts of antidote applied, relative to the herbicide, largelydepend on the type of application. If a field treatment is carried out,the ratio of the amount of antidote of the formula I to the amount ofphytotoxic chemical is 1:100 to 5:1 and preferably 1:20 to 1:1. In thecase of seed dressing and similar controlled protective measures,however, much smaller amounts of antidote are required relative to theamounts of herbicide which, for example, are subsequently used perhectare of cultivated area (for example about 1:3,000 to 1:1,000). As arule, there is only a loose relationship between protective measures,such as seed dressing with an antidote of the formula I, and possiblesubsequent field treatment with agricultural chemicals. Pre-treated seedand plants can subsequently come into contact with diverse chemicals inagriculture, horticulture and forestry.

The invention relates not only to agents which contain these oximeethers of the formula I together with herbicides but also to agentswhich contain these oxime ethers of the formula I as the sole activecomponent. It is possible to prepare, market or use plant protectionagents which contain an antidote of the formula I (also termed asafener), without the herbicide which is to be weakened (or anotheraggressive agricultural chemical) being present at the same time. Oneimportant application possibility is seed dressing, which is carried outat a time which is entirely independent of the use of the agriculturalchemical (for example herbicide). Another field of application is thetreatment of a soil which still contains residual amounts of a herbicidefrom the previous cultivation season, which could damage the intendednew plant crop.

The antidote characteristic is a substance characteristic which isindependent of the cultivated plant and of the agricultural chemicalwhich has the action which is to be selectively weakened and is acharacteristic which is inherent to a preparation of the formula I butbecomes evident only on interaction of the 3 componentsantidote/agricultural chemical/plant. Just as the pesticidal action of achemical which acts as a pesticide is evident only when a pest ispresent, the detection of the safener action also demands the presenceof the other two components which participate in the action, i.e. theagricultural chemical (for example the herbicide) and the cultivatedplant. This differentiates a formulated safener agent from a two- orthree-component mixture having a synergistic action, in which all theactive components are present at the same time and all have an actiondirected towards the same goal.

Within the framework of the present invention, cultivated plants are allplants which yield produce in any form (seeds, roots, stems, tubers,leaves, blossom and constituents such as oils, sugar, starch, proteinand the like) and are cultivated and tended for this purpose. Theseplants include, for example, all species of cereals, maize, rice,millet, soya, beans, peas, potatoes, vegetables, cotton, sugar beet,cane sugar, peanuts, tobacco and hops but also decorative plants, fruittrees and banana, cacao and natural rubber plants. This list imposes nolimitations. In principle, an antidote can be employed wherever acultivated plant is to be protected against the phytotoxicity of achemical.

The invention also relates to a process for protecting cultivated plantsagainst aggressive (phytotoxic) agricultural chemicals, by applying anoxime derivative of the formula I, which acts as an antidote, before orafter application of the agricultural chemical or at the same time asthe agricultural chemical, as desired.

The invention also relates to the propagation material of suchcultivated plants, which has been treated protectively with an oximederivative of the formula I. The term "propagation material" is to beunderstood as meaning all generative parts of plants which can be usedfor propagation of the cultivated plant. These include seed grains (seedin the narrower sense), roots, fruit, tubers, rhizomes, stem parts,branches (cuttings) and other parts of plants. However, they alsoinclude germinated plants and young plants which are to be furthertransplanted after germination or emergence. Young plants of this typecan be protected in a controlled manner by a complete or partialimmersion treatment before further transplanting.

The free oximes which fall within the scope of the formula I can beprepared by methods known per se for converting compounds of the formulaII

    Ar--CH.sub.2 --X                                           (II)

(in which the symbols are as defined under formula I) to the oxime byreaction with nitrous acid (HNO₂) or an organic or inorganic nitrite.They can also (depending on the substituent X) be obtained from ketocompounds of the formula III ##STR15## by reaction with hydroxylamine.

The free oximes obtained in this way can then, if desired, be convertedto the other derivatives which are included under the formula I andspecifically can, as desired, (a) be converted to the salts using basesor (b) be acylated with acids or acid halides or (c) be converted tooxime carbamates using isocyanates or carbamoyl halides or (d) beconverted to (thiolo)carbonates using halogenocarbonic acid (thio)estersor (e) be converted to other oxime ethers listed under Q using radicalswhich detach halogen or (f) be converted by means of COCl₂ to chlorides,which form carbamates with amines.

If the reactant carries a radical which detaches halogen, the free oximeis preferably employed in the form of a salt, preferably an alkali metalsalt.

With reference to the methods of preparation, the following literaturemay be cited: German Offenlegungsschrift No. 2,312,956; GermanOffenlegungsschrift 2,350,910; "Berichte der deutschen chem.Gesellschaft" 42, page 738 et seq. [1909]; J.f. prakt. Chemie 66, page353; Liebigs Ann. 250, 165 and Organic Reactions 1953, Volume 7, page343 and 373.

Solvents suitable for use in obtaining the compounds of the formula Iare, in principle, all solvents which are inert under the reactionconditions. Examples are hydrocarbons, but in particular polar solvents,such as acetonitrile, dioxan, Cellosolve, dimethylformamide, anhydrousacetic acid, pyridine and the like.

The temperatures are in the range of -20° to about 150° and preferablybetween 20° and 60°.

Substances which can be employed as the agents which detach hydrogenhalide are bases such as tertiary amines (triethylamine,triethylenediamine, N-methylpiperidine, N-methylmorpholine anddimethylaniline). In some cases, a suspension of anhydrous Na₂ CO₃ oranhydrous K₂ CO₃ in the anhydrous reaction medium or of NaOH solutionsunder phase transfer conditions suffices for this purpose.

Oximes exist in two stereoisomeric forms, the syn-form and theanti-form. All of the said end products have the formula I and can existin the two forms, as the pure compound or as mixtures. Within the scopeof the present description, accordingly, the compounds are to beunderstood as meaning the two stereoisomeric forms, on their own and asmixtures in any desired reciprocal mixing ratio.

The following examples illustrate the preparation of oxime derivativesof the formula I. The temperatures in the examples and in the followingtable are in degrees centigrade.

EXAMPLE 1

Preparation of the compound ##STR16##

6 g of 3,5-dibromo-2,4-dihydroxy-benzaldoxime were dissolved in 50 ml ofdimethylsulfoxide and a little diazabicyclooctane was added. 4 ml ofmethyl isocyanate were now added with cooling (<20° C.) and stirring andthe mixture was then stirred thoroughly at room temperature for 12hours. The reaction mixture was poured into ice-water and salted out.The suspension was filtered with suction, the residue was washed withwater and dissolved in a little dimethylformamide and active charcoalwas added to the solution.

This solution was filtered with suction and the end product wasprecipitated by adding water to the filtrate: 9 g of compound 198,melting point 131°-133° C.

EXAMPLE 2

Preparation of ##STR17##

12.3 g (0.1 mol) of 1-methyl-2-cyanomethyl-2-imidazoline are initiallyintroduced into 50 ml of glacial acetic acid. A solution of 7.8 g (0.1mol) of NaNO₂ in 20 ml of water is added dropwise at about 15°, withcooling. The mixture is stirred for 2 hours, cooled and filtered and theresidue is washed with a little cold water. This yields 11 g (=73% oftheory) of end product, which is recrystallised from methanol; meltingpoint 216.5° C.

EXAMPLE 3

Preparation of ##STR18##

17.1 g (0.1 mol) of 2-cyanomethyl-5-methylthio-1,3,4-thiadiazole areinitially introduced into 75 ml of glacial acetic acid. A solution of7.8 g (0.11 mol) of NaNO₂ in 20 ml of water is added dropwise and themixture is stirred for 1 hour. 200 ml of water are then added to thesolution and the mixture is filtered. The residue is washed with water:19 g (95% of theory) of end product, melting point >200° C.(decomposition).

EXAMPLE 4

Preparation of ##STR19##

A solution of 7.8 g (0.1 mol) of NaNO₂ in 20 ml of water is addeddropwise at room temperature to 17.4 g (0.1 mol) of2-cyanomethyl-benzthiazole in 50 ml of glacial acetic acid. The endproduct is filtered off after 2 hours and washed with water: 19.5 g (96%of theory), melting point >170° (decomposition).

EXAMPLE 5

Preparation of ##STR20##

36.7 g (0.2 mol) of 2-chloromethylbenzthiazole and 23.4 g (0.2 mol) ofisopentyl nitrite are initially introduced into 200 ml of dioxan. About0.4 mol of hydrogen chloride gas is passed in over a period of 30minutes, with cooling (<50° C.). After stirring for 2 hours, the mixtureis cooled and the end product is filtered off and washed with a littledioxan and then with petroleum ether: 39.5 g (93% of theory), meltingpoint 192°.

EXAMPLE 6

Preparation of ##STR21##

15.2 g (0.1 mol) of α-[1-methyl-imidazolin-2-yl]-α-oximino-acetonitrileand 6.4 g (0.11 mol) of methyl isocyanate are stirred in 200 ml of ethylacetate with a few drops of triethylamine for 16 hours. 16 g (76.5% oftheory) of end product are filtered off and this is washed with a littleethyl acetate; melting point 186°-190° C. (decomposition).

EXAMPLE 7

Preparation of ##STR22##

12 g (0.11 mol) of ethyl chloroformate are added dropwise to a solutionof 18.7 g (0.1 mol) of α-[benzoxazol-2-yl]-α-oximino-acetonitrile in 120ml of pyridine, with ice-cooling. After stirring for 3 hours, themixture is poured into 1 liter of ice-water and the residue is filteredoff and washed with water: 23 g (89% of theory) of end product, which isrecrystallised from acetonitrile; melting point 187° C.

EXAMPLE 8

Preparation of ##STR23##

9.7 g (0.05 mol) of the Na salt ofα-oximino-α-(4-cyanophenyl)-acetonitrile, 9.3 g (0.05 mol) ofiodoacetamide and 50 ml of acetonitrile are added together and themixture is stirred for 3 hours at 50°-60° and cooled to roomtemperature, whereupon the end product starts to precipitate out. Thesuspension is poured into ice-water and the residue is filtered off withsuction and washed with water and hexane: 9.2 g (80.7% of theory),melting point 197°-199° C.

EXAMPLE 9

Preparation of ##STR24##

9.6 g (0.05 mol) of the Na salt ofα-(3-cyanophenyl)-α-oximino-acetonitrile and 11.3 g (0.15 mol) ofchloroacetonitrile are heated in 50 ml of acetonitrile for 3 hours at50°-60°, with stirring. The suspension, which has become dark, isevaporated and water is added to the residue. The desired end product isextracted from this mixture with methylene chloride and this extract,after drying over Na sulfate and stirring with active charcoal, isfiltered to give a clear filtrate. The filtrate is evaporated: 7.7 g ofend product, melting point 93° C.

Compounds which can be prepared in this way or by one of the methodsindicated above are the following compounds of the formula

    __________________________________________________________________________     ##STR25##                                                                    Compound                              Melting                                 No.   R.sub.11  R.sub.12                                                                            R.sub.13                                                                            Q         point                                   __________________________________________________________________________    1     2-OH      3-Cl  5-Cl  H         193-197°                         2     4-OH      3-Cl  5-Cl  H         178-181°                         3     2-OH      4-Cl  H     H         123-124°                         4     2-OH      4-Br  H     H         126-127°                         5     2-OH      4-CH.sub.3                                                                          6-CH.sub.3                                                                          H         126.4-                                                                        127°                             6     3-OH      H     H     H         90-92°                           7     4-OH      H     H     H         95-99°                           8     2-OH      H     H     H         57-59°                           8a    4-OCONHCH.sub.3                                                                         H     H     CONHCH.sub.3                                      9     4-OCONHCH.sub.3                                                                         2-CH.sub.3                                                                          H     H         142-143°                         10    4-OH      2-CH.sub.3                                                                          6-C.sub.2 H.sub.5                                                                   H         142-146°                         11    2-OCONHCH.sub.3                                                                         H     H     H         133-135°                                                               (decom-                                                                       position)                               12    4-OCOCH.sub.3                                                                           2-NO.sub.2                                                                          3-OCH.sub.3                                                                         H         155-158°                         13    2-CONHCH.sub.3                                                                          H     H     CONHCH.sub.3                                                                            126-129°                         14    4-OH      3-Br  5-Br  COC.sub.2 H.sub.5                                                                       132-133°                         15    4-N(C.sub.2 H.sub.5).sub.2                                                              H     H     H         93-96°                           16    2-OCONHC.sub.6 H.sub.5                                                                  H     H     CONHC.sub.6 H.sub.5                                                                     233°                             17    2-OH      3-CH.sub.3                                                                          5-C.sub.4 H.sub.9 (t)                                                               H         109°                             18    4-OH      3-OCH.sub.3                                                                         H                                                                                    ##STR26##                                                                              117-118°                         19    2-NHCOC.sub.6 H.sub.5                                                                   H     H     H         157-159°                         20    2-OCONHCH.sub.3                                                                         H     H     H         159°                                                                   (decom-                                                                       position)                               21    2-OCOCH.sub.3                                                                           3-Cl  5-Cl  COCH.sub.3                                                                              114-116°                         22    4-OH      3-Cl  5-Cl  CONHCH.sub.3                                                                            160-162°                         23    2-OCONHCH.sub.3                                                                         4-CH.sub.3                                                                          6-CH.sub.3                                                                          CONHCH.sub.3                                                                            130-135°                         and also the following compounds of the formula                                ##STR27##                                                                    Compound                             Physical                                 No.    R.sub.14  R.sub.15                                                                           R.sub.16                                                                           Q         constant                                 __________________________________________________________________________    24     4-CN      H    H    COC.sub.6 H.sub.5                                                                       m.p.                                                                          147-150°                          25     4-CN      H    H    CH.sub.2 CONH.sub.2                                                                     m.p.                                                                          197-199°                          26     4-CN      H    H    CH.sub.2 CN                                                                             m.p.                                                                          133-136°                          27     4-CN      H    H                                                       nC.sub.3 H.sub.7                                                                     n.sub.D.sup.20 1.5609                                                  28     4-SO.sub.2 NH.sub.2                                                                     H    H    H         m.p. 236°                         29     4-OCF.sub.2 CHFCl                                                                       H    H    CH.sub.2 CN                                                                             oil                                      29a    3-CN      H    H    CH.sub.2 CN                                                                             m.p. 93°                          and also the following compounds of the formula                                ##STR28##                                                                    Compound                           Melting                                    No.           Y     Q              point                                      __________________________________________________________________________    30            S     H              167-168°                            31            S     CH(CH.sub.3)COOCH.sub.3                                                                      122-126°                            32            O     H              218-219°                            33            S     CONHC.sub.4 H.sub.9 (tert.)                                                                  192-202°                            34            O     CH.sub.2 CN    167-168°                            35            S     CH.sub.2COOCH.sub.3                                                                          173-174°                            36            O     CH(CH.sub.3)COOCH.sub.3                                                                      129-131°                            and also the following compounds of the formula                                ##STR29##                                                                    Compound                                                                      No.          Q                Physical constant                               __________________________________________________________________________    37           CH.sub.2CCH      melting point 56-58°                     38           CH.sub.2CN       oil                                             39           CH.sub.2CONH.sub.2                                                                             oil                                             40           CH.sub.2CCCH.sub.3                                                                             oil                                             41           CH.sub.2CHCH.sub.2                                                                             oil                                             42           CH.sub.2C(CL)CCl.sub.2                                                                         oil                                             43           CH.sub.2COOCH.sub.3                                                                            oil                                             44           CH.sub.2CHC(CH.sub.3)C.sub.2 H.sub.5                                                           n.sub.D.sup.20 1.5604                           45           CONHCH.sub.3     oil                                             46           CON(CH.sub.3).sub.2                                                                            oil                                             and also the following compounds of the formula                                ##STR30##                                                                    Compound                                                                      No.        Y   R.sub.21                                                                            R.sub.20                                                                           R.sub.22                                                                              Melting point                               __________________________________________________________________________    47         O   H     Cl   OCH.sub.3                                                                             155°                                 48         O   H     Cl   NHCH.sub.3                                                                            156°                                 49         O   Cl    H    NHCH.sub.3                                                                            211°                                 50         O   Cl    Cl   OCH.sub.3                                                                             182°                                 51         O   Cl    Cl   NHCH.sub.3                                                                            224°                                 52         O   Cl    H    OCH.sub.3                                                                             132°                                 53         S   H     Cl   NHCH.sub.3                                                                            186°                                 54         S   Cl    Cl   NHCH.sub.3                                                                            212°                                 and also the following compounds of the formula                                ##STR31##                                                                    Compound                            Melting                                   No.        R.sub.23   R.sub.24      point                                     __________________________________________________________________________    55         OC.sub.2 H.sub.5                                                                          COOC.sub.2 H.sub.5                                                                         99°                                56         OC.sub.3 H.sub.7 (iso)                                                                   COOC.sub.3 H.sub.7 (iso)                                                                    103°                               57         CH.sub.3   COCH.sub.3    127°                               58         CH.sub.3   CONHCH.sub.3  169°                               59         NHC.sub.2 H.sub.5                                                                        CONHC.sub.2 H.sub.5                                                                         152°                               60         NHC.sub.3 H.sub.7 (iso)                                                                  CONHC.sub.3 H.sub.7 (iso)                                                                   135°                               61         NHC.sub.3 H.sub.7 (n)                                                                    CONHC.sub.3 H.sub.7 (n)                                                                     142°                               62         NHC.sub.4 H.sub.9 (n)                                                                    CONHC.sub.4 H.sub.9 (n)                                                                     138°                               63         NHCH.sub.3 CONHCH.sub.3  141°                               64                                                                                        ##STR32##                                                                                ##STR33##    129°                               65         NHCH.sub.3 H             144°                               and also the following compounds of the formula                                ##STR34##                                                                    Compound                          Melting                                     No.    X        Q                 point                                       __________________________________________________________________________    66      CN      H                 170°                                                                   (decomposition)                             67     CN       Na.sup.+          (solid)                                     68     CN       CON(CH.sub.3).sub.2                                                                             200°                                 69     CN       COCH.sub.3        168°                                 70     CN       COOC.sub.3 H.sub.7 (iso)                                                                        186°                                 71     CN       SO.sub.2CH.sub.3  202°                                 72     CN       CONHCH.sub.3      164°                                 73     CN       COCHCHCH.sub.3    75°                                  74     CN       CH.sub.3          152°                                 75     CN       CH.sub.2CCH       118°                                 76     COOC.sub.2 H.sub.5                                                                     H                 120°                                                                   (decomposition)                             77     CN       CH.sub.2CN        207°                                 78     CN       CONHC.sub.6 H.sub.4Cl(4)                                                                        194°                                 79     CN       COC.sub.6 H.sub.3 Cl.sub.2 (2,4)                                                                190°                                                                   (decom-                                                                       position)                                   80     CN       CONHC.sub.6 H.sub.3 Cl(3)-CF.sub.3 (4)                                                          206°                                 81     CN       COC.sub.6 H.sub.4 Cl(4)                                                                         190°                                 82     Cl       H                 192°                                 83     Cl       CONHCH.sub.3                                                  84     Cl       CONHC.sub.6 H.sub.5                                           85     COOCH.sub.3                                                                            H                 124°                                                                   (decom-                                                                       position)                                   86     CN       CONHCH.sub.2CHCH.sub.2                                                                          130°                                 87     CN       SCH.sub.2CHCH.sub.2                                                                             117°                                 87a    CN       SO.sub.2C.sub.6 H.sub.5                                                                         204°                                 and also the following compounds of the formula                                ##STR35##                                                                    Compound                                                                      No.        X     Q               Melting point                                __________________________________________________________________________    88         CN    H               >270°                                                                  (decomposition)                              89         CN    Na.sup.+        (solid)                                      90         CN    CON(CH.sub.3).sub.2                                                                           >240°                                                                  (decomposition)                              91         CN    SO.sub.2 CH.sub.3                                                                             >210°                                                                  (decomposition)                              92         CN    CONHCH.sub.3    >210°                                                                  (decomposition)                              93         CN    COCH.sub.3      210°                                  94         CN    CH.sub.2CN      179°                                  95         CN    CONHC.sub.2 H.sub.5                                                                           285°                                  96         CN    CONHC.sub.3 H.sub.7 (n)                                                                       233°                                  97         CN    CONHC.sub.3 H.sub.7 (iso)                                                                     112°                                                                   (decomposition)                              98         CN    CONHC.sub.4 H.sub.9 (n)                                                                       238°                                                                   (decomposition)                              99         CN    CONHC.sub.4 H.sub.9 (tert.)                                                                   310°                                                                   (decomposition)                              100        CN    COC.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                              >250°                                                                  (decomposition)                              101        CN    CONHC.sub.6 H.sub.4 Cl(4)                                                                     >200°                                                                  (decomposition)                              102        Cl    CH.sub.2 CN                                                  103        Cl    CH.sub.2CCH                                                  104        Cl    CH.sub.2CHCH.sub.2                                           105        Cl    CH.sub.2CHCHCH.sub.3                                         106        CN    CH.sub.2CHCHCH.sub.3                                         107        CH.sub.3                                                                            CH.sub.2CHCHCH.sub.3                                         108        CN    CH.sub.2CONH.sub.2                                           and also the following compounds of the formula                                ##STR36##                                                                    Compound                                                                      No.    X        Q                 Melting point                               __________________________________________________________________________    109    CN       H                 220°                                                                   (decomposition)                             110    CN       COCH.sub.3        180°                                 110a   CN       COCH.sub.2 Cl                                                 111    CN       COOC.sub.2 H.sub.5                                                                              199°                                 112    CN       CON(CH.sub.3).sub.2                                                                             212°                                 113    CN       CONHCH.sub.3      >170°                                                                  (decomposition)                             114    CN       SO.sub.2 CH.sub.3 207°                                 115    CN       CH.sub.2 CCH      107°                                 116    COOC.sub.2 H.sub.5                                                                     H                 134°                                                                   (decomposition)                             117    COOCH.sub.3                                                                            H                 137°                                                                   (decomposition)                             118    CN       CH.sub.3          125°                                 119    CN       COOC.sub.3 H.sub.7 (iso)                                                                        179°                                 120    CN       COC.sub.4 H.sub.9 (n)                                                                           (solid)                                     121    CN       CON(CH.sub.3)OCH.sub.3                                                                          171°                                 122    CN       COOCH.sub.3       173°                                 123    CN       COC.sub.3 H.sub.7 (n)                                                                           96°                                  124    CN       COCHCHCH.sub.3    153°                                 124a   CN       COCHCH.sub.2                                                  125    CN       COSC.sub.2 H.sub.5                                                                              154°                                 126    CN       CONHCH.sub.2 CH.sub.2 Cl                                                                        150-155°                             127    CN       CONHCH.sub.2 Cl   165-168°                             128    CN       CH.sub.2CN        164°                                 129    CN       2-Furanoyl        230°                                 130    CN       COC.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                                >210°                                                                  (decomposition)                             131    CN       CONHC.sub.6 H.sub.3 Cl.sub.2 (3,5)                                                              197°                                 132    CN       COC.sub.6 H.sub.4 Cl(2)                                                                         145°                                 133    CN                                                                                      ##STR37##        200°                                 134    CN       COC.sub.6 H.sub.3 Cl.sub.2 (3,5)                                                                183°                                 135    CN       COC.sub.6 H.sub.4CH.sub.3 (2)                                                                   182°                                 136    CN       COC.sub.6 H.sub.4OCH.sub.3 (2)                                                                  166°                                 137    CN       CH.sub.2C.sub.6 H.sub.5                                                                         125°                                 138    Cl       H                 >180°                                                                  (decomposition)                             139    Cl       CONHC.sub.6 H.sub.5                                                                             167°                                 140    Cl       CONHCH.sub.3      >130°                                                                  (decomposition)                             141    Cl       CONHC.sub.6 H.sub.4 Cl(4)                                                                       188-193°                             142    CN       CONHCH.sub.2CHCH.sub.2                                                                          150°(de-                                                               composition)                                143    H        H                 167°                                 and also the following compounds of the formula                                ##STR38##                                                                    Compound                              Melting                                 No.   R.sub.17           R.sub.18                                                                           R.sub.19                                                                           Salt                                                                             point                                   __________________________________________________________________________    144   2-CHNOH            3-OH 6-CH.sub.3                                                                         -- (solid)                                 145   4-CHNOCONHCH.sub.3 2-Cl 6-Cl -- 156°                             146   4-CHNOH            2-Cl 6-Cl -- 183°                             147   3-CHNOH            2-Cl 6-Cl -- 219°                             148                                                                                  ##STR39##         2-Cl 6-Cl -- 156°                             149                                                                                  ##STR40##         H    H    -- 166°                             150   2-C(CH.sub.3)NOCOSC.sub.6 H.sub.5                                                                H    H    -- 78°                              151   4-C(Cl)NOH         H    H    HCl                                                                              >190°                                                                  (decom-                                                                       position)                               152   2-C(CH.sub.3)NOCONHCH.sub.3                                                                      H    H    -- 132°                             153   4-C(nC.sub.11 H.sub.23)NOCONHCH.sub.3                                                            H    H    -- 69°                              154   4-C(COOC.sub.4 H.sub.9 n)NOH                                                                     H    H    -- 186°                             155   2-C(CH.sub.3)NOH   H    H    -- 122°                             156   2-C(CH.sub.3)NOCOSC.sub.2 H.sub.5                                                                H    H    -- (oil)                                   157   4-C(CH.sub.3)NOCOSC.sub.2 H.sub.5                                                                H    H    -- (oil)                                   158   4-C(nC.sub.10 H.sub.23)NOH                                                                       H    H    -- 103°                             159   3-C(CH.sub.3)NOH   H    H    -- 115°                             160   4-C(CN)NOH         H    H    -- 284°                             161   2-CHNOCH.sub.2 CN  H    H    -- (oil)                                   162   2-CHNOCH.sub.2 CH.sub.2 Cl                                                                       H    H    -- (oil)                                   163   4-CHNOCH.sub.2 CH.sub.2 Cl                                                                       H    H    -- (oil)                                   and also the compound                                                         No. 164                                                                                 ##STR41##              Melting point 184°                    and also the compounds of the formula                                          ##STR42##                                                                    Compound                               Melting                                No.   X    R.sub.25 R.sub.26                                                                            R.sub.27                                                                           Q       point                                  __________________________________________________________________________    165   C.sub.2 H.sub.5                                                                    2-OCONHCH.sub.3                                                                        4-CH.sub.3                                                                          H    CONHCH.sub.3                                                                          131°                            166   nC.sub.3 H.sub.7                                                                   2-OCONHCH.sub.3                                                                        4-Cl  5-Cl CONHCH.sub.3                                                                          133°                            167   CH.sub.3                                                                           2-OCOCH.sub.3                                                                          4-Cl  6-Cl H       156°                            168   C.sub.2 H.sub.5                                                                    2-OCOCH.sub.3                                                                          4-Cl  6-Cl H       145°                            169   CH.sub.3                                                                           H        n-C.sub.10 H.sub.21 O                                                               H    H       79°                             170   CH.sub.3                                                                           4-C.sub.6 H.sub.4 F(p)                                                                 H     H    H       149°                            171   CH.sub.3                                                                           4-C.sub.6 H.sub.5                                                                      H     H    H       189°                            172   CH.sub.3                                                                           4-C.sub.6 H.sub.5CH.sub.2 O                                                            H     H    H       206°                            173   CH.sub.3                                                                           4-Cyclohexyl                                                                           H     H    H       118°                            174   CH.sub.3                                                                           4-C.sub.6 H.sub.5 (CH.sub.2).sub.3 O                                                   H     H    H       113°                            175   CH.sub.3                                                                           2-C.sub.6 .sub.5CH.sub.2 O                                                             H     H    H       114°                            176   CH.sub.3                                                                           4-C.sub.6 H.sub.4 Br(p)                                                                H     H    H       215-219°                        177   CH.sub.3                                                                           2-OH     4-Cl  6-Cl H       133°                            178   C.sub.2 H.sub.5                                                                    2-OH     4-Cl  6-Cl H       98°                             179   nC.sub.3 H.sub.7                                                                   2-OH     4-Cl  6-Cl H       155°                            180   C.sub.2 H.sub.5                                                                    2-OH     4-Cl  H    H       83°                             181   C.sub.2 H.sub.5                                                                    4-OH     3-CH.sub.3                                                                          5-CH.sub.3                                                                         H       148-                                                                          154°                            182   nC.sub.3 H.sub.7                                                                   2-OH     4-Cl  5-Cl H       121°                            183   C.sub.2 H.sub.5                                                                    2-OH     4-CH.sub.3                                                                          H    H       105°                            184   CH.sub.3                                                                           2-OH     H     5-Cl H       169°                            185   C.sub.2 H.sub.5                                                                    2-OH     H     5-CH.sub.3                                                                         H       140°                            186   CH.sub.3                                                                           2-OH     H     5-Cl CH.sub.2 CN                                                                           98°                             and also the following compounds of the formula                                ##STR43##                                                                    Compound                              Melting                                 No.    R.sub.25  R.sub.26   Q         point                                   __________________________________________________________________________    187    CONHC.sub.2 H.sub.5                                                                     CONHC.sub.2 H.sub.5                                                                      CONHC.sub.2 H.sub.5                                                                     138°                             188     CONHC.sub.6 H.sub.5                                                                    CONHC.sub.6 H.sub.5                                                                      CONHC.sub.6 H.sub.5                                                                     (solid)                                 189    CONHC.sub.4 H.sub.9 (n)                                                                 CONHC.sub.4 H.sub.9 (n)                                                                  CONHC.sub.4 H.sub.9 (n)                                                                 152-                                                                          160°                             190                                                                                   ##STR44##                                                                               ##STR45##                                                                                ##STR46##                                        191    CONHCH.sub.3                                                                            CH.sub.2CHCH.sub.2                                                                       CONHCH.sub.3                                      192    CONHC.sub.2 H.sub.5                                                                     CH.sub.2CHCH.sub.2                                                                       CONHC.sub.2 H.sub.5                               193    CONHC.sub.6 H.sub.5                                                                     CH.sub.2CHCH.sub.2                                                                       CONHC.sub.6 H.sub.5                               194    CONHCH.sub.3                                                                            CH.sub.3CCH                                                                              CONHCH.sub.3                                      195    CONHC.sub.2 H.sub.5                                                                     CH.sub.2CCH                                                                              CONHC.sub.2 H.sub.5                               196    CONHC.sub.6 H.sub.5                                                                     CH.sub.2CCH                                                                              CONHC.sub.6 H.sub.5                               197    CH.sub.3  CH.sub. 3  COCH.sub.2 Cl                                                                           101-103°                         198    CONHCH.sub.3                                                                            CONHCH.sub.3                                                                             CONHCH.sub.3                                                                            133°                             and also the following compounds of the formula                                ##STR47##                                                                    Compound                                                                      No.            Q                 Melting point                                __________________________________________________________________________    199            H                 135-136°                              200            CONHCH.sub.3      130°                                  201            CONHC.sub.3 H.sub.7 (n)                                                                         118°                                  202            CONHCH.sub.2 CH.sub.2Cl                                                                         167-171°                              203            CON(CH.sub.3).sub.2                                                                             120-128°                              and also the following compounds of the formula                                ##STR48##                                                                    Compound                           Melting                                    No.    X       R.sub.28                                                                              Q           point                                      __________________________________________________________________________    204    CN      CH.sub.3S                                                                             H           >200°                                                                  (decomposition)                            205    CN      C.sub.2 H.sub.5O                                                                      H           193°                                                                   (decomposition)                            206    CN      CH.sub.3S                                                                             CH.sub.2CN  111°                                207    CN      CH.sub.3S                                                                             CH(CH.sub.3)COOCH.sub.3                                                                   96°                                 208    CN      C.sub.2 H.sub.5O                                                                      CH.sub.2CN  (semi-solid)                               209    CN      C.sub.2 H.sub.5O                                                                      CH(CH.sub.3)COOCH.sub.3                                                                   58-63°                              210    Cl      C.sub.6 H.sub.5                                                                       H           222°                                                                   (decomposition)                            211    Cl      CH.sub.3S                                                                             H           187°                                212    Cl      CH.sub.3SO.sub.2                                                                      H           187°                                                                   (decomposition)                            213    COOC.sub.2 H.sub.5                                                                    CH.sub.3 O                                                                            H           151-156°                            214    COOC.sub.2 H.sub.5                                                                    CH.sub.3 S                                                                            H           130°                                                                   (decomposition)                            215    COOC.sub.2 H.sub.5                                                                    CH.sub.3 SO                                                                           H           134°                                                                   (decomposition)                            216    COOCH.sub.3                                                                           CH.sub.3 S                                                                            H                                                      216a   COOCH.sub.3                                                                           CH.sub.3 SO                                                                           H           138°                                                                   (decomposition)                            and also the following compounds of the formula                                ##STR49##                                                                    Compound                                                                      No.        R.sub.29                                                                            Q               Melting point                                __________________________________________________________________________    217        CH.sub.3                                                                            H               216.5°                                218        H     H               >250°(de-                                                              composition)                                 219        CH.sub.3                                                                            CONHCH.sub.3    186-190°                                                               (decomposition)                              220        CH.sub.3                                                                            2-Furanoyl      153-157°                                                               (decomposition)                              221        CH.sub.3                                                                            CH.sub.2 CN     94-96°                                222        CH.sub.3                                                                            CH(CH.sub.3)COOCH.sub.3                                                                       (oil)                                        223        CH.sub.3                                                                            CH.sub.2CHCH.sub.2                                           224        CH.sub.3                                                                            CH.sub.2CHCHCH.sub.3                                         225        CH.sub.3                                                                            CH.sub.2CCH                                                  226        CH.sub.3                                                                            CH.sub.2CONH.sub.2                                           and also the following compounds of the formula                                ##STR50##                                                                    Compound                                                                      No.      R.sub.30 R.sub.31         Melting point                              __________________________________________________________________________    227      H                                                                                       ##STR51##       165° (decomposition)                228      H                                                                                       ##STR52##       68-82°                              229      C.sub.6 H.sub.3 Cl.sub.2 (2,4)                                                         CHNOH            163°                                230      C.sub.6 H.sub.3 Cl.sub.2 (2,4)                                                         CHNOC(CH.sub.3)COOCH.sub.3                                                                     59-65°                              231      C.sub.6 H.sub.4 Cl(4)                                                                  CHNOH            140°                                232      C.sub.6 H.sub.4 Cl(4)                                                                  CHNOC(CH.sub.3)COOCH.sub.3                                                                     (semi-                                                                        solid)                                     and also the following compounds of the formula                                ##STR53##                                                                    Compound                          Melting                                     No.      n  R.sub.32                                                                              R.sub.33                                                                          R.sub.34  point                                       __________________________________________________________________________    233      1  CH.sub.3                                                                              H   CHNOH     228°                                                                   (decomposition)                             234      1  CH.sub.3                                                                              Cl  CHNOH     145-7°                               235      1  C.sub.6 H.sub.5                                                                       H   CHNOH     208-209°                             236      0  COOCH.sub.3                                                                           H   C(Cl)NOH  166°                                                                   (decomposition)                             and also the following compounds of the formula                                ##STR54##                                                                    Compound                            Melting                                   No.         R.sub.35                                                                              Q               point                                     __________________________________________________________________________    237         tert.C.sub.4 H.sub.9                                                                  H               101-105°                           238         tert.C.sub.4 H.sub.9                                                                  CON(CH.sub.3).sub.2                                                                           190°                               239         CH.sub.3                                                                              H               204°                               240         CH.sub.3                                                                              CON(CH.sub.3).sub.2                                                                           194°                               241         Cl      H               208°                               242         Cl      CON(CH.sub.3).sub.2                                                                           177°                               243         CH.sub.3                                                                              CH.sub.2CN                                                244         CH.sub.3                                                                              CH.sub.2CHCHCH.sub.3                                      and also the following compounds of the formula                                ##STR55##                                                                    Compound                        Melting                                       No.          R.sub.36                                                                            Q            point                                         __________________________________________________________________________    245          CH.sub.3                                                                            H            223°                                   246          CH.sub.3                                                                            CON(CH.sub.3 ).sub.2                                                                       211°                                   247          NO.sub.2                                                                            H            122-124°                                                               (decomposition)                               248          NO.sub.2                                                                            CON(CH.sub.3).sub.2                                                                        about 180°                             249          CH.sub.3                                                                            CH.sub.2 CN  solid                                         250          CH.sub.3                                                                            CH.sub.2CHCH.sub.2                                                                         solid                                         251          CH.sub.3                                                                            CH.sub.2CCH  solid                                         and also the following compounds                                              No. 252                                                                                 ##STR56##              melting point 100°                    No. 253                                                                                 ##STR57##              melting point 107°                    No. 254                                                                                 ##STR58##              solid                                        No.255                                                                                  ##STR59##              Melting point 122°                              ##STR60##                                                           No. 256  Q = H                   Melting point 108°                    No. 257  Q = CONHCH.sub.3        Melting point 185°                    No. 258  Q = CON(CH.sub.3).sub.2 Melting point 95°                     No. 259                                                                                 ##STR61##              Melting point 138-141°                No. 260                                                                                 ##STR62##              Melting point 203-205°                No. 261                                                                                 ##STR63##              Melting point 235°                    No. 262                                                                                 ##STR64##              Boiling point 90-130°                 No. 263                                                                                 ##STR65##              Melting point 99-105°                 and also the following compounds of the formula                                ##STR66##                                                                    Compound                            Physical                                  No.          R.sub.37      Q        constant                                  __________________________________________________________________________    264          H             C.sub.2 H.sub.5                                                                        oil                                       265          CH.sub.2C.sub.6 H.sub.5                                                                     C.sub.2 H.sub.5                                                                        oil                                       266          CH.sub.2C.sub.6 H.sub.4 Cl(2)                                                               C.sub.2 H.sub.5                                                                        oil                                       267          CH.sub.2C.sub.6 H.sub.5                                                                     C.sub.4 H.sub.9 (n)                                                                    oil                                       268          CH.sub.2C.sub.6 H.sub.4 Cl(2)                                                               C.sub.4 H.sub. 9 (n)                                                                   oil                                       and also the following compounds of the formula                                ##STR67##                                                                    Compound                          Physical                                    No.        R.sub.38                                                                            R.sub.39                                                                            X          constant                                    __________________________________________________________________________    269        H     H     CN                                                     270        Br    H     CN         oil                                         271        Br    H     CH.sub.3   oil                                         272        H     H     CH.sub.3   melting point                                                                 93-108°                              273        H     Cl    CH.sub.3                                               274        H     Cl    COOCH.sub.3                                            275        H     Cl    COOCH.sub.3                                            276        H     Cl    CON(CH.sub.3).sub.2                                    277        H     Cl    Cl                                                     278        Br    H     Cl         oil                                         279        Cl    Cl    Cl         oil                                         and also the compounds                                                        No. 280                                                                             ##STR68##                   melting point 59-65°                 No. 281                                                                             ##STR69##                   solid                                       No. 282                                                                             ##STR70##                                                               __________________________________________________________________________

As already mentioned, various methods and techniques are possible forthe use of the compounds of the formula I for protecting cultivatedplants against agricultural chemicals:

1. Seed dressing

(a) Dressing of the seeds with an active substance formulated as awettable powder, by shaking in a vessel until the formulation isuniformly distributed on the surface of the seed (dry dressing). About10 to 500 g of the active substance of the formula I (40 g to 2 kg ofwettable powder) are used per 100 kg of seed.

(b) Dressing of the seeds with an emulsion concentrate of the activesubstance of the formula I according to method (a) (wet dressing).

(c) Dressing by immersing the seed in a liquor containing 50-3,200 ppmof the active substance of the formula I for 1-72 hours and, if desired,subsequently drying the seed (immersion dressing).

Dressing of the seed or treatment of the germinated young seedling are,of course, the preferred methods of application, because the treatmentwith the active substance is directed entirely towards the intendedcrop. As a rule 10 g to 500 g and preferably 50 to 250 g of activesubstance are used per 100 kg of seed and, depending on the method,which also enables other active substances or micronutrients to beadded, it is possible to use concentrations in excess of or below theindicated limiting concentrations (repeat dressings).

(2) Application from a tank mixture

A liquid formulation of a mixture of antidote and herbicide (reciprocalratio between 1:20 and 5:1) is used and the amount of herbicide appliedis 0.1 to 6 kg per hectare. A tank mixture of this type is preferablyapplied before or immediately after sowing or is worked into the as yetunsown soil to a depth of 5-10 cm.

(3) Application into the seed furrow

The antidote is introduced, in the form of an emulsion concentrate orwettable powder or as granules, into the open sown seed furrow and,after covering the seed furrow in the normal way, the herbicide is thenapplied by the pre-emergence process.

Thus, in principle, the antidote can be applied before, together with orafter the pesticide and can be used on the seed or on the field beforeor after sowing or in certain cases also after germination of the seed.

(4) Controlled release of the active substance

The active substance is absorbed, as a solution, on mineral granulecarriers or polymerised granules (urea/formaldehyde) and allowed to dry.If desired a coating can be applied (coated granules) which enables theactive substance to be released in a metered manner over a specificperiod.

Of course, all other methods for application of active substances canalso be employed. Examples of these are given below.

The compounds of the formula I can be used on their own or together withsuitable carriers and/or other additives. Suitable carriers andadditives can be solid or liquid and correspond to the substancescommonly used in formulation technology, for example natural orregenerated mineral substances, solvents, dispersing agents, wettingagents, adhesives, thickeners, binders or fertilisers.

The content of active substance in marketable agents is between 0.1 and90%.

For application, the compounds of the formula I can be in the followingprocessing forms (the percentages by weight in brackets representingadvantageous amounts of active substance):

Solid processing forms: dusts and sprinkling agents (up to 10%),granules, coated granules, impregnated granules and homogeneous granulesand pellets (grains) (1 to 80%);

Liquid processing forms:

(a) active substance concentrates which are dispersible in water:wettable powders and pasts (25-90% in commercial packs and 0.01 to 15%in ready-to-use solutions); and emulsions concentrates and solutionconcentrates (10 to 50%; 0.01 to 15 in ready-to-use solutions);

(b) solutions (0.1 to 20%) and aerosols.

The active substances of the formula I of the present invention can beformulated, for example, as follows:

Dusts

The following substances are used to formulate (a) 5% and (b) a 2% dust:

(a)

5 parts of active substance

95 parts of talc;

(b)

2 parts of active substance

1 part of highly dispersed silicic acid

97 parts of talc.

The active substances are mixed with the carriers and ground and in thisform can be processed to dusts for application.

Granulate

The following substances are used to formulate a 5% granulate:

5 parts of active substance

0.25 part of epichlorohydrin

0.25 part of cetyl polyglycol ether

3.50 parts of polyethylene glycol

91 parts of kaolin (particle size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and the mixture isdissolved in 6 parts of acetone. Then polyethylene glycol and cetylpolyglycol ether are added. The resultant solution is sprayed on kaolinand the acetone is then evaporated in vacuo. A microgranulate of thistype can advantageously be worked into seed furrows.

Wettable powders

The following constituents are used to formulate (a) 70%, (b) a 40%, (c)and (d) a 25% and (e) a 10% wettable powder:

(a)

70 parts of active substance

5 parts of sodium dibutylnaphthylsulfonate

3 parts of naphthalenesulfonic acid/phenolsulfonic acid/formaldehydecondensate (3:2:1)

10 parts of kaolin

12 parts of Champagne chalk

(b)

40 parts of active substance

5 parts of sodium ligninsulfonate

1 parts of sodium dibutylnaphthalenesulfonate

(c)

54 parts of silicic acid

25 parts of active substance

4.5 parts of calcium ligninsulfonate

1.9 parts of Champagne chalk/hydroxyethylcellulose mixture (1:1)

1.5 parts of sodium dibutylnaphthalenesulfonate

1.5 parts of silicic acid

19.5 parts of Champagne chalk

28.1 parts of kaolin

(d) 25 parts of active substance

2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol

1.7 parts of a Champagne chalk/hydroxyethylcellulose mixture (1:1)

8.3 parts of sodium aluminum silicate

16.5 parts of kieselguhr

46 parts of kaolin

(e)

10 parts of active substance

3 parts of a mixture of the sodium salts of saturated fatty alcoholsulfates

5 parts of naphthalensulfonic acid/formaldehyde condensate

82 parts of kaolin.

The active substances are intimately mixed in suitable mixers with theadditives and ground in appropriate mills and rollers. Wettable powdersof excellent wettability and suspension power are obtained. Thesewettable powders can be diluted with water of give suspensions of thedeisred concentration and can be used in particular for dressing seedsand for the immersion treatment of cuttings.

Emulsifiable concentrate

The following substances are used to formulte a 25% emulsifiableconcentrate:

25 parts of active substance

2.5 parts of epoxidised vegetable oil

10 parts of an alkylarylsulfonate/fatty alcohol polyglycol ether mixture

5 parts of dimethylformamide

57.5 parts of xylene.

By diluting such a concentrate with water it is possible to prepareemulsions of any desired concentration, which are especially suitablefor dressing seeds and for the immersion treatment of young plants.

Pre-emergence antidote test (basic test) General test method

Small flow pots (diameter 6 cm at the top) are filled with garden soilinto which the plant seed is sown, covered with the soil and gentlypressed firm. The substance to be tested as an antidote is then sprayedin the form of a dilute solution (obtained from a wettable powder) in anamount corresponding to 4 kg of active substance/ha. The herbicide issprayed onto the soil directly afterwards in corresponding amount. Afterthe pots have stood for 18 days at about 20°-23° C. and 60-70% relativeatmospheric humidity, evaluation is made in accordance with a linearscale from 1 to 9, 1 denoting total damage to the plant and 9 denotingundamaged healthy plant. Plants without antidote protection are used ascontrol.

The following herbicides and plants were employed:

(1) 1.5 kg/ha of the active substanceα-[4-(p-trifluoromethylphenoxy)-phenoxy]-propionic acid n-butoxyethylester in maize of the "Orla 264" variety.

(2) 1.5 kg/ha of the active substanceMetolachlor=N-(1-methyl-2-methoxyethyl)-N-chloroacetyl-2-ethyl-6-methylanilinein sorghum of the "Funk G-522" variety.

(3) 2 kg/ha of the active substancePrometryn=2,4-bis(isopropylamino)-6-methylthio-s-triazine in soybeans.

(4) 2 kg/ha of the active substance4-ethylamino-6-tert.-butylamino-2-chloro-s-triazine in wheat of the"Farnese" variety.

(5) 4 kg/ha of the active substancePrometryn=2,4-bis(iospropylamino)-6-methylthio-s-triazine in sorghum ofthe "Funk G:522" variety.

(6) 2 kg/ha of the active substanceα-[4-(p-trifluoromethylphenoxy)-phenoxy]-propionic acid n-butoxyethylester in barley of the "Mazurak" variety.

Compounds of the formula I give a good antidote action in these tests.The following results are given by way of example.

    ______________________________________                                                 Compound    Rating of the herbicidal influence                       Test variant                                                                           No.         (without/with antidote)                                  ______________________________________                                        4        280         2/5                                                      5        234         6/8                                                      6        209         6/8                                                      6        163         4/6                                                      6        272         3/8                                                      5        175         3/6                                                      5        174         3/5                                                      5         87a        3/6                                                      5        101         1/6                                                      5        199         1/6                                                      5        234         6/8                                                      2        198         2/8                                                      3         16         3/5                                                      4         29a        2/7                                                      2        281         3/5                                                      4        281         2/4                                                      5        824         2/6                                                      5         124a       1/5                                                      ______________________________________                                    

Antidote Action on Separate Application (Antidote/Pre-emergence,Herbicide/Post-emergence) General Test Method

Small flower pots (diameter 6 cm at the top) are filled with sandy loamsoil into which the plant seed is sown. After covering the seed, thesubstance to be tested as an antidote is sprayed onto the surface, inthe form of a dilute solution and in an amount which, when converted,corresponds to 4 kg of active substance/ha. The pots are kept at 20°-23°C. and 60-70% relative atmospheric humidity. When the plants havereached the 2- to 3-leaf stage after 10 days, they are treated, asindicated below, with the corresponding amount of herbicide. 14 daysafter application of the herbicide, evaluation is made in accordancewith a linear scale from 1 to 9,1 denoting total damage to the plant and9 denoting undamaged healthy plant. Plants without antidote protectionare used as control.

The herbicides and plants used are:

(1) 4.0 kg/ha of the active substanceAmetryn=2-ethylamino-4-isopropylamino-6-methylthio-s-triazine in maizeof the "Orla 264" variety.

(2) 1.0 kg/ha of the active substancePrometryn=2,4-bis-(isopropylamino)-6-methylthio-s-triazine in sorghum ofthe "Funk G-522" variety.

(3) 0.25 kg/ha of the active substanceα-[4-(p-trifluoromethylphenoxy)-penoxy]-propionic acid n-butoxyethylester in barley of the "Mazurka" variety.

Compounds of the formula I showed a good antidote action in these tests.

Antidote Action in Transplanted Rice on Separate Application(Antidote/Pre-emergence, Herbicide/Post-emergence)

Plastic tubs (8×8 cm, 10 cm high) are filled with wet marshy soil to 2cm below the edge. The substance to be tested as an antidote is sprayed,as a dilute solution, onto the surface of the soil in an amountcorresponding to 4 kg of active substance/ha. Rice plants of the "Ir-88"variety are transplanted in the 11/2- to 2-leaf stage into the preparedtubs. On the next day, the water level is raised to about 1.5 cm. Fourdays after transplantation2-ethylamino-4-(1,2-dimethyl-n-propylamino)-6-methylthio-s-triazine isadded to the water in granule form in an amount which, when converted,corresponds to 0.75 kg of active substance/ha. During the test period,the temperature is 26°-28° C. and the relative atmospheric humidity60-80%. 20 days after the treatment with herbicide, evaluation is madein accordance with a linear scale from 1 to 9, 1 denoting total damageto the plant and 9 denoting undamaged healthy plant. Plants notprotected with antidote are used as control.

Good antidote results were obtained with the compounds of the formula I.The following results are given by way of example.

    ______________________________________                                                    Rating of the herbicidal influence                                Compound No.                                                                              (without/with antidote)                                           ______________________________________                                        245         5/7                                                               235         3/8                                                               259         5/8                                                               234         3/5                                                                16         2/6                                                               272         3/5                                                                65         4/7                                                                87a        4/6                                                               184         5/7                                                               128         5/7                                                                77         5/8                                                                94         5/7                                                               228         4/7                                                               ______________________________________                                    

Pre-emergence Antidote Test in Nutrient Solution

A Hewitt nutrient solution, which contains the amount of herbicideindicated below as well as 10 ppm of the antidote to be tested, isprepared.

Seeds which would normally be expected to be damaged in the indicatedtest concentrations of the herbicide employed are used and sown ingranular zonolith (expanded vermiculite) in a plastic flower pot(diameter 6 cm at the top) which is perforated at the bottom. This potis then placed in a second transparent plastic flower pot (diameter 7 cmat the top) which contains about 50 ml of the nutrient solutionpreparedwith herbicide and antidote. This nutrient solution then risesby capillary action in the filling material of the smaller pot andmoistens the seed and the germinating plant. The loss in fluid is dailyreplenished to 50 ml with pure Hewitt nutrient solution. 3 weeks afterthe start of the test, evaluation is made in accordance with a linearscale from 1 to 9, 1 denoting total damage to the plant and 9 denotingundamaged healthy plant. The control solution employed in the paralleltest contains no added antidote.

The herbicides and plants employed are:

(1) 4 ppm of Prometryn=2,4-bis(iospropylamino)-6-methylthio-s-trizine insorghum of the "Funk G-522" variety.

(2) 4 ppm of 4-ethylamino-6-tert.-butylamino-2-chloro-s-triazine inwheat of the "Farnese" variety.

(3) 4 ppm of α-[4-(p-trifluoromethylphenoxy)-phenoxy]-propionic acidn-butoxyethyl ester in barley of the "Mazurka" variety.

(4) 5 ppm ofMetolachlor=N-(1-methyl-2-methoxyethyl)-N-chloroacetyl-2-ethyl-6-methylanilinein sorghum of the "Funk G-522" variety.

A good antidote action is obtained with the compounds of the formula I.The following results are given by way of example:

    ______________________________________                                                 Compound    Rating of the herbicidal influence                       Test variant                                                                           No.         (without/with antidote)                                  ______________________________________                                        4        227         4/6                                                      1        151         2/4                                                      1        269         2/6                                                      1        198         1/7                                                      2        198         1/4                                                      2        282         2/6                                                      4        211         5/8                                                      1        170         2/5                                                      1        174         2/4                                                      1        109         2/5                                                      3        111         2/7                                                      3        114         5/8                                                      3        110         5/7                                                      4        259         2/4                                                      2        197         1/3                                                      ______________________________________                                    

Pre-emergence antidote test in nutrient solution (rice)

A Hewitt nutrient solution is prepared which additionally contains 10ppm of the antidote to be tested.

Rice seed of the "IR-8" variety is sown in inert filling material(granular zonolith) in a plastic flower pot (diameter 6 cm at the top)which is perforated at the bottom. This pot is placed in a secondtransparent plastic flower pot (diameter 7 cm at the top) which containsabout 50 ml of the prepared nutrient solution; this nitrient solutionthen rises by capillary action in the filling material of the smallerpot and moistens the seed and the germinating plant. The loss in fluidis daily replenished to 50 ml with pure Hewitt nutrient solution. After15 days the rice plants are transplanted in the 2- to 21/2-leaf stageinto rectangular plastic tubs (8×8 cm, 10 cm high) which are filled with500 ml of wet marshy soil. On the next day the water level in these tubsis raised to 1-2 cm above the base level. 4 days after transplantation,the herbicide2-ethylamino-4-(1,2-dimethyl-n-propylamino)-6-methylthio-s-triazine isadded in granule form and in an amount which, when converted,corresponds to 0.75 kg of active substance/ha. 3 weeks after adding theherbicide, evaluation is made in accordance with a linear scale from 1to 9, 1 denoting total damage to the plant and 9 denoting undamageshealthy plant. The control solution employed in the parallel testcontains no added antidote. Compounds of the formula I showed anantidote action in this test.

Post-emergence antidot test in nutrient solution General test method

Small plastic flower pots (diameter 6 cm at the top), which areperforated at the bottom, are filled with granular zonolith and theseeds are sown in this material. The pot is then placed in a secondtransparent plastic flower pot (diameter 7 cm at the top) which contains50 ml of water which rises by capillary action and moistens the seed.From the 5th day, the continual loss in water is made up with Hewittnutrient solution. From the 15th day, when the plant is in the 11/2- to2-leaf stage, 10 ppm of the antidote to be tested and the amount ofherbicide indicated below are added to the nutrient solution which hasagain been replenished to 50 ml. From the 16th day, the loss in fluid isagain made up with pure Hewitt nutrient solution. During the entireduration of the test, the temperature is 20°-23° C. and the relativeatmospheric humidity 60-70%.

3 weeks after the addition of the herbicide and of the antidote,evalution is made in accordance with a linear scale from 1 to 9, 1denoting total damage to the plant and 9 denoting undamaged healthyplant.

Test Variants

(1) 15 ppm of α-[4-(3,5-dichloropyridyl)-2-oxy)-phenoxy]-propionic acidpropargylthiolo-ester in wheat of the "Zenith" variety.

(2) 4 ppm of 4-ethylamino-6-tert.-butylamino-2-chloro-s-triazine inwheat of the "Zenith" variety.

(3) 2 ppm of α-[4-(p-trifluoromethylphenoxy)-phenoxy]-propionic acidn-butoxyethyl ester in maize of the "Orla" variety.

(4) 8 ppm of α-[4-(p-trifluoromethylhenoxy)-phenoxy]-propionic acidn-butoxyethyl ester in sorghum of the "Funk G-522" variety.

(5) 4 ppm of Prometryn=2,4-bis(isopropylamino)-6-methylthio-s-triazinein sorghum of the "Funk G-522" variety.

(6) 8 ppm of α-[4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-propionic acidmethyl ester in wheat of the "Zenith" variety.

Compounds of the formula I give a good antidote action in these tests.The following results are given by way of example:

    ______________________________________                                                 Compound    Rating of the herbicidal influence                       Test variant                                                                           No.         (without/with antidote)                                  ______________________________________                                        5        170         1/3                                                      1        209         3/5                                                      5         71         2/4                                                      1        160         3/6                                                      1        242         3/7                                                      1        222         6/8                                                      5        151         1/4                                                      1        207         6/8                                                      ______________________________________                                    

Antidote test--seed soaking

Rice seeds of the IR-8 variety are immersed for 48 hours in solutions ofthe test substances in concentrations of 10 or 100 ppm. The seeds arethen allowed to dry for about 2 hours until they are no longer tacky.Rectangular plastic tubs (8×8 cm, 10 cm high) are filled with sandy loamto 2 cm below the edge. 4 g of seeds are sown in each tub and only veryloosely covered (to about the diameter of the seed). The soil is kept ina moist (non-marshy) state. The herbicideN-(1-methyl-2-methoxyethyl)-N-chloroacetyl-2-ethyl-6- methylaniline orN-propoxyethyl-N-chloroacetyl-2,6-diethylaniline, as desired, is thenapplied as a dilute solution and in an amount which, when converted,corresponds to 1.5 kg of active substance/ha. 18 days aftertransplantation, evaluation is made in accordance with a linear scalefrom 1 to 9, 1 denoting total damage to the plant and 9 denotingundamaged healthy plant.

Compounds of the formula I show a good antidote action in this test. Thefollowing results are given by way of example.

    ______________________________________                                               Compound                                                                              Rating of the herbicidal influence                                    No.     (without/with antidote)                                        ______________________________________                                        100  ppm       8a      3/6                                                    10   ppm       8a      3/6                                                    10   ppm      7        3/6                                                    10   ppm     281       2/6                                                    10   ppm     282       3/5                                                    10   ppm      23       4/6                                                    10   ppm     151       2/6                                                    10   ppm     257       4/6                                                    10   ppm     174       2/4                                                    10   ppm      66       2/4                                                    10   ppm     109       2/5                                                    100  ppm     111       2/4                                                    10   ppm     113       3/7                                                    100  ppm     113       3/6                                                    100  ppm      53       3/7                                                    10   ppm      53       3/5                                                    10   ppm      93       3/6                                                    10   ppm      110a     3/6                                                    10   ppm      84a      3/6                                                    10   ppm     199       2/6                                                    100  ppm      95       3/6                                                    100  ppm      97       3/6                                                    100  ppm      99       3/7                                                    100  ppm     186       2/6                                                    10   ppm     220       3/6                                                    ______________________________________                                    

What is claimed is:
 1. A compound of the formula ##STR71## wherein R₂₈is lower alkoxy, lower alkylthio, lower alkylsulfinyl, loweralkylsulfonyl or phenyl,Q is hydrogen; lower alkyl which can beinterrupted by oxygen or sulfur, or substituted by halogen or cyano; oran aliphatic carboxylic acyl radical, and X is hydrogen, cyano, halogen,C₁ -C₁₀ alkyl, lower alkanoyl, --COOH, --COO--lower alkyl, --COS--loweralkyl, or --CON(R)₂ in which R is hydrogen or lower alkyl.
 2. A compoundaccording to claim 1 wherein X is cyano, halogen or COO--lower alkyl. 3.The compound according to claim 2 which is ##STR72##
 4. The compoundaccording to claim 2 which is ##STR73##
 5. The compound according toclaim 2 which is ##STR74##
 6. A compound of the formula ##STR75##according to claim 2.